CN106280839B - Epoxy group-fluorinated acrylate polymer coating agent preparation method - Google Patents
Epoxy group-fluorinated acrylate polymer coating agent preparation method Download PDFInfo
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- CN106280839B CN106280839B CN201610621811.2A CN201610621811A CN106280839B CN 106280839 B CN106280839 B CN 106280839B CN 201610621811 A CN201610621811 A CN 201610621811A CN 106280839 B CN106280839 B CN 106280839B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/002—Pretreatement
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/102—Pretreatment of metallic substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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Abstract
The present invention relates to a kind of epoxy group-fluorinated acrylate polymer coating agent preparation method of application on the steel plate, by perluorooctyl acrylate, acrylic ester compound and methyl propenoic acid glycidyl ether copolyreaction, epoxy group-fluorinated acrylate polymer is obtained.Including following synthesis step: (1) preparation of perluorooctyl acrylate；(2) epoxy group-fluoro-acrylate copolymer preparation.Epoxy group-fluoro-acrylate copolymer prepared by the present invention carries out heat cure with the steel plate containing amido functional group, compared to presently commercially available waterproofing agent of organosilicon, has more excellent water and oil repellant and resistance to wiping.
Description
Technical field
The invention belongs to substrate surface treatment fields, are related to the fluorine-containing material that free radical addition preparation has epoxy group
Material, the epoxy group-fluorinated acrylate polymer coating agent preparation method of especially a kind of application on the steel plate.
Background technique
With social progress and development, steel plate materials are very extensive always in our life, and to steel board
The performance requirement of material is also increasingly enhanced, we not only need a large amount of steel material in industrial aspects such as automobile, space flight, buildings,
Steel material is also indispensable in daily family life.In the stainless steel material in kitchen and bathroom, it will usually will
Water stain and grease stain is stained with material surface, therefore the Water-proof and oil-proof, the antifouling and wear-resisting performance that improve steel plate are extremely important.Mesh
Before, it is known that technology be occurred by fluorochemical monomer and coating functional group reactions introduce fluorine element reduce the surface of film can, mention
Its high hydrophobic and oleophobic performance.But individually the adhesion property of the coating agent containing fluorine element and substrate surface is bad, rub resistance
Performance is low.
Summary of the invention
The object of the present invention is to provide a kind of epoxy group-fluorinated acrylate polymer coating agent of application on the steel plate
Preparation method, solve surface of steel plate Water-proof and oil-proof and it is wear-resisting the problems such as.
Realize the object of the invention technical solution:
A kind of epoxy group-fluorinated acrylate polymer coating agent preparation method applied on the steel plate, passes through propylene
Sour ten trifluoro monooctyl esters, acrylic ester compound and methyl propenoic acid glycidyl ether copolyreaction, obtain epoxy group-fluorine-containing third
Olefin(e) acid ester copolymer.Epoxy group-fluorinated acrylate polymer is dissolved in a solvent by certain mass score, is made into coating
Agent.
Specific step is as follows:
(1) preparation of perluorooctyl acrylate
By a certain amount of acrylic acid, hydroquinone, ten trifluoro octanols and catalyst in container, at 60-100 DEG C 4~12
Hour.After reaction, temperature is reduced to room temperature, first uses the NaOH solution washed product of 3wt%, then production is washed with water repeatedly
Object, separates organic phase, and vacuum distillation removes solvent, obtains perluorooctyl acrylate, sealed storage；
(2) epoxy group-fluoro-acrylate copolymer preparation
By perluorooctyl acrylate, acrylic ester compound and methyl propenoic acid glycidyl ether by certain mole
Than feeding intake in container, a small amount of initiator and solvent is added, in 60-110 DEG C of stirring a few hours, is cooled to room temperature, stops anti-
It answers.Vacuum distillation removes solvent, obtains yellow transparent liquid, i.e. products therefrom.
Wherein CH2Ra is H, CH in=C (Ra) COORb3；Rb is CH3, CH2CH3, CH2CH2CH2CH3。
Moreover, catalyst described in step (1) be sulfuric acid, it is butyl titanate, p-methyl benzenesulfonic acid, solid acid catalyst, miscellaneous more
Acid catalyst.
Moreover, acrylic ester compound described in step (2) be methyl acrylate, ethyl acrylate, butyl acrylate,
Methyl methacrylate, ethyl methacrylate, butyl methacrylate, γ-methacryloxypropyl trimethoxy silicon
Alkane.
Moreover, initiator described in step (2) is azodiisobutyronitrile, dibenzoyl peroxide, 4,4 '-bis- (tert-butyls
Cyclohexyl) peroxy dicarbonate, potassium peroxydisulfate, ammonium persulfate.
Moreover, solvents tetrahydrofurane, toluene, ethyl acetate, butyl acetate, hexone described in step (2)
One or more of mixing.
A kind of application method of epoxy group-fluorinated acrylate polymer coating agent, steps are as follows:
(1) steel plate pre-processes: cleaning steel plate, after cleaning that amino silicone toluene of the steel plate immersion containing 1wt% is molten
Liquid 30min places into the drying of vacuum oven high temperature, for use；
(2) coating agent is prepared: dissolving epoxy group-fluorinated acrylate polymer with solvent, preparing mass fraction is 5%
Coating agent；Or epoxy group-fluorinated acrylate polymer and γ-glycidyl ether oxygen propyl trimethoxy silicon are dissolved with solvent
Alkane, being configured to γ-glycidyl ether oxygen propyl trimethoxy silicane mass fraction is 3%, epoxy group-fluorine-containing polyisocyanate polyaddition
The coating agent that amount of substance score is 5%；
(3), by prepared coating agent, spraying on the steel plate, places 10-15min at room temperature, then moves to vacuum drying
Case, 130~160 DEG C of placement 30-50min, film-forming.
The solvent be one of tetrahydrofuran, toluene, ethyl acetate, butyl acetate, hexone or
Two or more mixtures.
The cleaning steel plate is by ethyl alcohol-acetone ultrasonic cleaning or UV- ozone irradiation cleaning or plasma
Reason.
In order to solve surface of steel plate Water-proof and oil-proof and it is wear-resisting the problems such as, this patent utilize ten trifluoro octanols, acrylic acid
It is function monomer with allyl glycidyl ether, has synthesized epoxy group-fluoro-acrylate copolymer coating agent.On the steel plate first
It is handled with γ-aminopropyl triethoxysilane, passes through self-assembling method shape using the hydroxyl on amino silicone and steel plate
It is at relatively thin molecular film, then by high temperature that amino silicone hydrolytic crosslinking is fixed on the steel plate.Then by epoxy group-fluorine-containing third
Olefin(e) acid ester copolymer is compounded with γ-glycidyl ether oxygen propyl trimethoxy silicane, and spraying is on the steel plate, it is therefore an objective to make epoxy
Base with and amino solidification, improve the adhesive force of coating to be fixed on steel plate.
The advantages and positive effects of the present invention are as follows:
Epoxy group-fluoro-acrylate copolymer prepared by the present invention carries out heat cure with the steel plate containing amido functional group,
Compared to presently commercially available waterproofing agent of organosilicon, there is more excellent water and oil repellant and resistance to wiping.
Specific embodiment
Below by specific embodiment, the invention will be further described, and it is not limit that following embodiment, which is descriptive,
Qualitatively, this does not limit the scope of protection of the present invention.
Embodiment 1:
The synthesis of perluorooctyl acrylate
2g acrylic acid, 0.05g hydroquinone, ten trifluoro octanol of 9g and 0.22g p-methyl benzenesulfonic acid are added in container, 80
DEG C stirring 6h.It is cooled to room temperature, with the NaOH solution washed product of 3wt%, is washed with distilled water repeatedly 3 times, stand liquid separation.It will
Organic phase vacuum distillation, obtains perluorooctyl acrylate, stores, for use.
Embodiment 2:
Copolymer S1 preparation
In the three-necked flask equipped with reflux condensing tube and dropping funel, 0.3g methyl propenoic acid glycidyl is first added
Ether, 10g perluorooctyl acrylate, 0.1g butyl acrylate and 0.5g azodiisobutyronitrile and 20ml toluene solvant, in nitrogen
The lower 80 DEG C of stirrings of gas shielded.Simultaneously by 0.6g methyl propenoic acid glycidyl ether, 20g perluorooctyl acrylate, 0.2g propylene
Acid butyl ester and 1g azodiisobutyronitrile after mixing, move in dropping funel.Mixture is added dropwise while stirring, time for adding is
2h；After being added dropwise, 4h is kept the temperature.Solvent is removed under reduced pressure.Obtain copolymer S1.
Embodiment 3:
Copolymer S2 preparation
Method is same as Example 2.Do not exist together is to change azodiisobutyronitrile into dibenzoyl peroxide.
Embodiment 4:
Copolymer S3 preparation
In the three-necked flask equipped with reflux condensing tube and dropping funel, 0.6g methyl propenoic acid glycidyl is first added
Ether, 10g perluorooctyl acrylate, 0.2g butyl acrylate and 0.5g azodiisobutyronitrile and 20ml toluene solvant, in nitrogen
The lower 80 DEG C of stirrings of gas shielded.Simultaneously by 1.2g methyl propenoic acid glycidyl ether, 20g perluorooctyl acrylate, 0.4g propylene
Acid butyl ester and 1.1g azodiisobutyronitrile after mixing, move in dropping funel.Mixture, time for adding are added dropwise while stirring
For 2h；After being added dropwise, 4h is kept the temperature.Solvent is removed under reduced pressure.Obtain copolymer S3.
Embodiment 5:
Copolymer S4 preparation
In the three-necked flask equipped with reflux condensing tube and dropping funel, the toluene of 20ml is first added, is warming up to 110 DEG C,
Under nitrogen protection, it is added dropwise by 0.9g methyl propenoic acid glycidyl ether, 30g perluorooctyl acrylate, 0.3g acrylic acid fourth
The mixture of ester and 1.5g azodiisobutyronitrile composition, time for adding 2h；After being added dropwise, 4h is kept the temperature.It is removed under reduced pressure
Solvent.Obtain copolymer S4.
Steel plate pretreatment:
Steel plate is cleaned, steel plate is immersed into the amino silicone toluene solution 30min containing 1wt% after cleaning, then put
Enter the drying of vacuum oven high temperature, for use.
Coating agent is prepared:
Coating agent 1:
It dissolves S1, S2, S3, S4 copolymer respectively with ethyl acetate, prepares the coating agent that mass fraction is 5% respectively.It will
Prepared coating agent on the steel plate that is sprayed on that treated, places 10-15min at room temperature.Then vacuum oven is moved to, it is high
Temperature places 30-50min film-forming.
Coating agent 2:
It is answered with ethyl acetate dissolution copolymer and Z-6040 (γ-glycidyl ether oxygen propyl trimethoxy silicane)
Match, when to be configured to γ-glycidyl ether oxygen propyl trimethoxy silicane mass fraction be 3%, copolymer quality score is 5%
Prepared coating agent on the steel plate that is sprayed on that treated, is placed 10-15min by coating agent at room temperature.Then it is dry to move to vacuum
Dry case, high temperature place 30-50min film-forming.
Application experiment:
For contact angle with JC2000C contact angle measurement (upper marine morning) test water droplet in sample surfaces, volume of often dripping is 1
μ L, 25 DEG C of test temperature.
Friction testing: it is rubbed using the rub resistance testing machine (BYD) of NMC-02D model to the coating on steel plate
Test, using 0000# rhinoceros board steel wool as friction medium, friction stroke 20mm, rub 60 times/min of rate, loads in 700g
Lower reciprocating friction.
Application experiment result such as the following table 1:
Table 1
Claims (3)
1. a kind of application method of the epoxy group for steel plate-fluorinated acrylate polymer coating agent, it is characterised in that: cleaning
Steel plate is immersed the amino silicone toluene solution 30min containing 1wt% after cleaning, placed into vacuum oven by steel plate
High temperature drying is stand-by；Coat agent compounding method are as follows: dissolve epoxy group-fluorinated acrylate polymer with solvent and γ-shrink is sweet
Oily ether oxygen propyl trimethoxy silicane, being configured to γ-glycidyl ether oxygen propyl trimethoxy silicane mass fraction is 3%, epoxy
The coating agent that base-fluorinated acrylate polymer mass fraction is 5%；By prepared coating agent, spray on the steel plate, room temperature
Then lower placement 10-15 min moves to vacuum oven, 130 ~ 160 DEG C of placement 30-50min, film-forming；The epoxy
The specific preparation method of base-fluorinated acrylate polymer is: in the three-necked flask equipped with reflux condensing tube and dropping funel,
0.3g methyl propenoic acid glycidyl ether, 10g perluorooctyl acrylate, 0.1g butyl acrylate and 0.5g azo two is first added
Isobutyronitrile and 20ml toluene solvant, under nitrogen protection 80 DEG C stirring, while by 0.6g methyl propenoic acid glycidyl ether,
20g perluorooctyl acrylate, 0.2g butyl acrylate and 1g azodiisobutyronitrile after mixing, move in dropping funel,
Mixture, time for adding 2h are added dropwise while stirring；After being added dropwise, 4h is kept the temperature, solvent is removed under reduced pressure, obtains epoxy group-and contains
Fluoroacrylate polymer.
2. according to the method described in claim 1, it is characterized by: the perluorooctyl acrylate the preparation method comprises the following steps:
2g acrylic acid, 0.05g hydroquinone, ten trifluoro octanol of 9g and 0.22g p-methyl benzenesulfonic acid are added in container, 80 DEG C are stirred
6h is mixed, is cooled to room temperature, with the NaOH solution washed product of 3wt%, is washed with distilled water repeatedly 3 times, liquid separation is stood, it will be organic
It is mutually evaporated under reduced pressure, obtains perluorooctyl acrylate.
3. according to the method described in claim 1, it is characterized by: the solvent in coating agent preparation is tetrahydrofuran, toluene, second
One or more mixtures of acetoacetic ester, butyl acetate, hexone.
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| CN108250351A (en) * | 2017-03-12 | 2018-07-06 | 杨记 | A kind of preparation method and application of high temperature resistant color inhibition fluorine-containing epoxy resin |
| CN107880701A (en) * | 2017-12-11 | 2018-04-06 | 安徽大学 | A kind of self-cleaning anti-pollution paint of paper grade (stock) and preparation method thereof |
| CN109023923A (en) * | 2018-07-09 | 2018-12-18 | 合肥洁诺医疗用品有限公司 | It is a kind of to protect the preparation method for taking non-woven fabrics |
| CN108911983B (en) * | 2018-07-09 | 2021-04-02 | 济南齐氟新材料技术有限公司 | Environment-friendly preparation method of fluorine-containing acrylate |
| CN112552768B (en) * | 2020-12-17 | 2022-10-21 | 北京信为兢创科技有限公司 | Color developing coating composition |
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Effective date of registration: 20200409 Address after: 510653 Room 302, No.1 daguanzhong Road, Tianhe District, Guangzhou City, Guangdong Province Patentee after: Guangzhou runao chemical materials Co., Ltd Address before: Suining County in Jiangsu province 221200 Xuzhou peach chemical park north of Shahe on the west side of Zhu Guan Lu Xu Patentee before: XUZHOU YOUJI CHEMICAL MATERIAL Co.,Ltd. |
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